CN104549381A - Active silicon-phosphorus-aluminum material and application thereof - Google Patents
Active silicon-phosphorus-aluminum material and application thereof Download PDFInfo
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Abstract
The invention provides an active silicon-phosphorus-aluminum material. The material is characterized by having a pseudo-boehmite crystal-phase structure, and the anhydrous compound composition of the material is (0-0.2)Na2O.(64-76)Al2O3.(23-35)SiO2.(1-7)P2O5 based on an oxide weight ratio. The active silicon-phosphorus-aluminum material serving as a macromolecular cracking active element or active substrate material can be applied to the preparation process of a catalytic cracking catalyst or auxiliary, and has an excellent heavy oil cracking performance and excellent coke selectivity.
Description
Technical field
The present invention relates to a kind of mesopore activity silicon phosphor-aluminum material and application thereof, specifically about a kind of activated silica phosphor-aluminum material of effective raising heavy oil conversion performance and the application in catalytic cracking reaction process thereof.
Background technology
Catalytic cracking is as a kind of oil refining process, be widely used in refining of petroleum industry, as the course of processing of paramount importance in crude oil secondary processing, this technique is the main means of production of liquefied petroleum gas (LPG), gasoline, kerosene and diesel oil, occupies very important status in refinery.In catalytic cracking and hydrocracking process, the residual oil of heavy ends as vacuum distillate or more heavy constituent reacts in the presence of a catalyst, be converted into the gaseous cracked product of below gasoline, distillate and other liquid cracking products and four lighter carbon, usually need to use the catalytic material with high cracking activity in these reaction process.
Micro-pore zeolite catalytic material has excellent shape selective catalysis performance due to it and very high cracking reaction is active, is widely used in refining of petroleum and processing industry.Along with the requirement of the aspect of exhaustion and environment protection etc. day by day of petroleum resources; particularly crude oil becomes heavy rising tendency (high boiling component of >500 DEG C increases) and market increasingly to the heavy demand of light-end products; the deep processing to heavy oil and residual oil is more and more paid attention in refining of petroleum industry; part refinery starts to mix refining vacuum residuum, and even direct take long residuum as cracking stock.Traditional micro porous molecular sieve catalytic material due to its duct less, larger raw molecule is demonstrated and significantly limits diffusion, apparent reaction activity is caused to reduce, greatly limit macromolecular catalyzed reaction, be therefore not suitable for the catalytic cracking reaction being applied to the heavy ends such as heavy oil and residual oil.
For improving the heavy oil selectivity of catalytic cracking, the macromole of heavy oil fraction must be made to transform, also will reduce the further conversion of intermediate oil and petroleum naphtha simultaneously, this just needs to use aperture larger, diffusional limitation is not had to reactant molecule, and there is the material of higher cracking activity.And traditional micro porous molecular sieve is only beneficial to micromolecular cracking, therefore mesoporous and research and development that are macropore catalytic material are more and more subject to people's attention.
The appearance of mesopore molecular sieve is in 1992, first succeeds in developing (Beck J S, Vartuli J Z by Mobil company of the U.S., Roth W J et al., J.Am.Chem.Comm.Soc., 1992,114,10834-10843), called after M41S series mesopore molecular sieve, comprise MCM-41(Mobil Corporation Material-41) and MCM-48 etc., the aperture of molecular sieve can reach 1.6 ~ 10nm, evenly adjustable, and pore size distribution is concentrated, specific surface area and pore volume are large, high adsorption capacity; But the hole wall structure due to this molecular sieve analog is undefined structure, therefore hydrothermal stability difference and acidity is more weak, cannot meet the operational condition of catalytic cracking, industrial application is very restricted.
For solving the problem of mesopore molecular sieve hydrothermal stability difference, part research work concentrates on and improves molecular sieve pores wall thickness, and as adopted neutral template can obtain the thicker molecular sieve of hole wall, but the more weak shortcoming of acidity still exists.In CN1349929A, disclose a kind of novel mesopore molecular sieve, in molecular sieve hole wall, introduce the primary and secondary structural unit of zeolite, make it have the basic structure of traditional zeolite molecular sieve, this mesopore molecular sieve has the hydrothermal stability of strongly-acid and superelevation.But the deficiency of this molecular sieve is to use expensive template, and only there is about 2.7nm in aperture, still has larger space steric effect for macromole cracking reaction, and under high-temperature water heat condition, structure is easily subsided, and cracking activity is poor.
In catalytic cracking field, silica-alumina material has stronger acid sites and good cracking performance due to it and is applied widely.The proposition of mesoporous concept, again for the preparation of new catalyst provides possibility, current result of study focuses mostly on and is using expensive organic formwork agent and organosilicon source, and majority will through high-temperature water heat treatment process.Disclose a kind of monodisperse mesoporous aluminium silicon composite material in US5051385, add alkali after first acid mineral aluminium salt and silicon sol being mixed, obtain the aluminium content of silica-alumina material at 5 ~ 40 heavy %, aperture is between 20 ~ 50nm, and specific surface area reaches 50 ~ 100m
2/ g.Method disclosed in US4708945 is load silicon oxide particle or hydrated silica on porous boehmite, again by gained mixture in more than 600 DEG C hydrothermal treatment consists, obtained silica supported catalyzer on class boehmite surface, the surface-area of this material is 100 ~ 200m
2/ g, mean pore size 7 ~ 7.5nm.In US4440872, disclose serial sour cracking catalyst, the carrier of some of them catalyzer is by γ-Al
2o
3upper dipping silane, then obtained after 500 DEG C of roastings or steam-treated.US2394796 discloses and flood silicon tetrachloride or tetraethyl silicane on porous hydrated aluminum oxide, then obtains aluminium silicon composite material through hydrolysis.Adopt inorganic aluminate and water glass to be raw material in CN1353008A, form stable silicon-aluminum sol clearly through processes such as precipitation, dispergation, obtain white gels by drying, under 350 DEG C ~ 650 DEG C conditions, roasting obtained Si-Al catalysis material after 1 ~ 20 hour.US6858555 discloses a kind of mixed metal oxide that contains as the catalyst for cracking heavy oil of sieve and silica-sesquioxide, and wherein sieve and silica-sesquioxide is undefined structure.A kind of alumina gel being dispersed with silicon, boron, phosphorous oxides, VIII and group vib metal oxide is disclosed in CN1138566A, it mainly adopts organoaluminum source, silicon source, boron source and soluble sources to be raw material and is dissolved in Organic Alcohol solution, add organic formwork agent to be again hydrolyzed and gelation, gained mesoporous gel can be used as support of the catalyst, acid catalyst or hydrogenation catalyst and uses.
In CN1565733A, disclose a kind of mesoporous silica-alumina materials, this silica-alumina material has pseudo-boehmite crystal phase structure, and pore size distribution is concentrated, and specific surface area is 200 ~ 400m about
2/ g, pore volume 0.5 ~ 2.0ml/g, mean pore size is between 8 ~ 20nm, and most probable pore size is 5 ~ 15nm.The preparation of this mesoporous silica-alumina materials does not need to use organic formwork agent, and synthesis cost is low, and the silica-alumina material obtained has high cracking activity and hydrothermal stability, shows good macromole cracking performance in catalytic cracking reaction.
Summary of the invention
The object of the invention is a kind of activated silica phosphor-aluminum material is provided on the basis of existing technology and its preparation method is provided.
The present inventor finds on the basis of great many of experiments, when in mesopore activity silicon phosphor-aluminum material phosphorus being introduced the formation of mesoporous silicon aluminum, special matching relationship is there is between silicon, phosphorus, aluminium three kinds of component concentrations, appropriate amount scope is there is in phosphorus content under specific sial ratio, when it is applied in catalyst for heavy oil catalytic cracking or auxiliary agent, demonstrate more excellent heavy oil cracking performance.Based on this, form the present invention.
Activated silica phosphor-aluminum material provided by the invention, has pseudo-boehmite crystal phase structure, and its anhydrous compound composition counts (0-0.2) Na with oxide weight ratio
2o(64-76) Al
2o
3(23-35) SiO
2(1-7) P
2o
5, this material specific surface area is 300 ~ 500m
2/ g, preferably 350 ~ 450m
2/ g, pore volume is 0.5 ~ 1.5cm
3/ g, preferably 0.7 ~ 1.3cm
3/ g, mean pore size is 8 ~ 15nm, preferably 9 ~ 12nm.
Present invention also offers the preparation method of above-mentioned activated silica phosphor-aluminum material, it is characterized in that comprising following process, by the solution of aluminium source and a kind of alkali mixed plastic the pH value controlling plastic is 7 ~ 11 at room temperature to 85 DEG C; According to SiO
2: Al
2o
3=1:(1.8 ~ 3.5) weight ratio in plastic, add silicon source, ageing 1 ~ 5 hour at room temperature to 90 DEG C; By ageing gained solid sediment and ammonium salt or acid solution contact pairs, obtain sodium content lower than 0.3 % by weight solid sediment; Dry with phosphorus source contact pairs and at 100 DEG C ~ 150 DEG C again, or further, roasting at 500 DEG C ~ 700 DEG C, wherein said phosphorus source is with P
2o
5the weight ratio of the butt of meter, its charging capacity and silicon phosphor-aluminum material is (0.01 ~ 0.07): 1.
In said preparation method, aluminium source used comprises any one in the inorganic aluminium sources such as aluminum nitrate, Tai-Ace S 150 or aluminum chloride; Alkali used comprises any one in ammoniacal liquor, potassium hydroxide, sodium hydroxide or sodium metaaluminate, and silicon source used comprises any one in water glass, water glass, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon or silicon oxide.
In said preparation method, the solid sediment of said ageing gained and the process of ammonium salt contact pairs, be well known to those skilled in the art, its preferred process be by the solid sediment of ageing gained by throw out (butt): ammonium salt: H
2o=1:(0.1 ~ 1): the weight ratio of (5 ~ 30) exchanges 1 ~ 3 time at room temperature to 100 DEG C, exchanges 0.5 ~ 1 hour at every turn, until in solid sediment sodium content lower than 0.3%.Said ammonium salt comprise in ammonium chloride, ammonium sulfate, ammonium nitrate, volatile salt and bicarbonate of ammonia one or more.
In said preparation method, the solid sediment of said ageing gained and the process of acid solution contact pairs, be by the solid sediment of ageing gained by throw out (butt): acid: H
2o=1:(0.03 ~ 0.3): the weight ratio of (5 ~ 30) at least exchanges 0.2 hour at room temperature to 100 DEG C.The acid of using in said acid solution contact pairs process is generally mineral acid, can be selected from sulfuric acid, hydrochloric acid or nitric acid.
In said preparation method, said with phosphorus source contact pairs, its process can have multiple.Preferred process comprises gained solid sediment by throw out (butt): H
2o=1:(5 ~ 20) weight ratio mix with water and pull an oar, then add in above-mentioned slurries by phosphorus source, at room temperature to 90 DEG C, contact pairs 0.2 ~ 5 hour, preferably 0.5 ~ 3 hour, filters washing; Preferred process also can be that gained solid sediment is direct and phosphorus source is mixed in proportion, and grinding evenly.After above-mentioned two kinds of said processes with phosphorus source contact pairs, to need at 100 DEG C ~ 150 DEG C dry 10 ~ 20 hours and optionally, roasting at 500 DEG C ~ 700 DEG C, preferably roasting time can also be had to be the step of 1 ~ 4 hour.Said phosphorus source can be ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate or phosphoric acid.
Activated silica phosphor-aluminum material provided by the invention has pore property significantly, can as the active component of macromole cracking or active matrix material, with Y zeolite, kaolin, binding agent etc. with the use of being applied in catalytic cracking catalyst or auxiliary agent, its adding proportion can make the appropriate adjustments according to the change of stock oil character, operating procedure.When it is applied in catalyst for heavy oil catalytic cracking or auxiliary agent, while the coke selectivity that maintenance is good, catalyzer demonstrates more excellent heavy oil cracking performance.
Accompanying drawing explanation
Accompanying drawing is the X-ray diffraction spectrogram of embodiment 1 activated silica phosphor-aluminum material.
Embodiment
The following examples illustrate the present invention further, but content not thereby limiting the invention.
In embodiments, Na in sample
2o, Al
2o
3, SiO
2, P
2o
5content with x-ray fluorescence method measure (see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish).Sample thing adopts X-ray diffraction method to measure mutually.Sample specific surface area, pore volume, mean pore size are measured by nitrogen absorption under low temperature-desorption method.
Embodiment 1
This example illustrates the preparation of activated silica phosphor-aluminum material provided by the invention.
With concentration 90gAl
2o
3the Al of/L
2(SO
4)
3solution and concentration 102gAl
2o
3the NaAlO of/L, Crater corrosion 1.7
2solution is reaction raw materials, and flows plastic and regulate plastic pH=10.5, collects quantitative plastic slurries, adds concentration 60gSiO in proportion under stirring
2the water glass of/L, is warming up to 60 DEG C of ageings 3 hours; Use NH
4cl solution presses throw out (butt): ammonium salt: H
2the weight ratio of O=1:1:10, at 60 DEG C to sial throw out carry out ion-exchange removing sodium ion, and with a large amount of deionized water drip washing to sodium oxide content lower than 0.3 % by weight; Then gained solid sediment is pressed throw out (butt): H
2the weight ratio of O=1:10 mixes with water pulls an oar, and presses P
2o
5: the weight ratio of material butt=0.015:1 adds phosphoric acid, then reacts 2 hours at 50 DEG C, and after filtering washing, at 120 DEG C, namely drying obtains mesopore activity silicon phosphor-aluminum material provided by the invention for 10 hours.Be designated as MAM-1.
MAM-1 has pseudo-boehmite crystal phase structure, and its X-ray diffraction spectrogram as shown in Figure 1; Its elementary analytical chemistry consists of 0.10Na
2o74.8Al
2o
323.5SiO
21.5P
2o
5; Specific surface area 447m
2/ g, pore volume 1.21cm
3/ g, mean pore size 10.8nm.
Embodiment 2
This example illustrates the preparation of activated silica phosphor-aluminum material provided by the invention.
Preparation process is with embodiment 1.Wherein Secondary ammonium phosphate is selected in phosphorus source, and additional proportion is P
2o
5: material butt=0.031:1, react 2 hours at 60 DEG C, filtration is washed and namely drying obtains mesopore activity silicon phosphor-aluminum material provided by the invention for 10 hours at 120 DEG C.Be designated as MAM-2.
MAM-2 has pseudo-boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1; Its elementary analytical chemistry consists of 0.10Na
2o70.6Al
2o
326.1SiO
23.0P
2o
5; Specific surface area 409m
2/ g, pore volume 1.06cm
3/ g, mean pore size 10.3nm.
Embodiment 3
This example illustrates the preparation of activated silica phosphor-aluminum material provided by the invention.
Preparation process is with embodiment 1.Wherein primary ammonium phosphate is selected in phosphorus source, and additional proportion is P
2o
5: material butt=0.052:1, react 2 hours at 70 DEG C, filtration is washed and namely drying obtains mesopore activity silicon phosphor-aluminum material provided by the invention for 10 hours at 120 DEG C.Be designated as MAM-3.
MAM-3 has pseudo-boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1; Its elementary analytical chemistry consists of 0.08Na
2o67.3Al
2o
327.3SiO
25.1P
2o
5; Specific surface area 373m
2/ g, pore volume 1.07cm
3/ g, mean pore size 11.5nm.
Embodiment 4
This example illustrates the preparation of activated silica phosphor-aluminum material provided by the invention.
First by quantitative concentrations 90gAl
2o
3the Al of/L
2(SO
4)
3solution is placed in beaker, is dropwise added by ammoniacal liquor with vigorous stirring, until system pH=9.5, gelling temperature is 40 DEG C; Add concentration 60gSiO more under agitation
2the water glass of/L, is warming up to 60 DEG C of ageings 3 hours; Gained solid sediment is pressed throw out (butt): HCl:H
2the weight ratio of O=1:0.06:10 exchanges 30 minutes at 60 DEG C, filters washing and makes sodium oxide content lower than 0.3%; Then gained solid sediment is pressed throw out (butt): H
2the weight ratio of O=1:8 mixes with water pulls an oar, and presses P
2o
5: the weight ratio of material butt=0.046:1 adds Secondary ammonium phosphate, then reacts 1 hour at 60 DEG C, to filter after washing at 120 DEG C dry 10 hours, more namely roasting obtains mesopore activity silicon phosphor-aluminum material provided by the invention for 2 hours at 550 DEG C.Be designated as MAM-4.
MAM-4 has pseudo-boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1; Its elementary analytical chemistry consists of 0.08Na
2o64.8Al
2o
330.5SiO
24.5P
2o
5; Specific surface area 392m
2/ g, pore volume 1.25cm
3/ g, mean pore size 12.8nm.
Embodiment 5
This example illustrates the preparation of activated silica phosphor-aluminum material provided by the invention.
Preparation process is with embodiment 4.Wherein phosphorus source introducing adopt dipping method, namely direct by sodium oxide content lower than 0.3% solid sediment and phosphoric acid press P
2o
5: the weight ratio mixing of material butt=0.025:1, namely obtains mesopore activity silicon phosphor-aluminum material provided by the invention for 10 hours in 120 DEG C of dryings after grinding evenly.Be designated as MAM-5.
MAM-5 has pseudo-boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1; Its elementary analytical chemistry consists of 0.08Na
2o72.5Al
2o
324.8SiO
22.5P
2o
5; Specific surface area 365m
2/ g, pore volume 0.83cm
3/ g, mean pore size 9.1nm.
Embodiment 6
This example illustrates the preparation of activated silica phosphor-aluminum material provided by the invention.
Preparation process is with embodiment 4.Wherein phosphorus source introducing adopt dipping method, namely direct by sodium oxide content lower than 0.3% solid sediment and ammonium phosphate with P
2o
5: the weight ratio mixing of material butt=0.065:1, in 120 DEG C of dryings 10 hours after grinding evenly, more namely roasting obtains mesopore activity silicon phosphor-aluminum material provided by the invention for 2 hours at 600 DEG C.Be designated as MAM-6.
MAM-6 has pseudo-boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1; Its elementary analytical chemistry consists of 0.07Na
2o69.0Al
2o
324.3SiO
26.6P
2o
5; Specific surface area 338m
2/ g, pore volume 0.94cm
3/ g, mean pore size 11.1nm.
Comparative example 1
The process of preparation process as described in CN1565733A of this comparative example.
With concentration 90gAl
2o
3the Al of/L
2(SO
4)
3solution and concentration 102gAl
2o
3the NaAlO of/L, Crater corrosion 2.5
2solution is reaction raw materials, and flows plastic and regulate plastic pH=9.5, is gathered into rubber cement liquid, adds concentration 60gSiO in proportion under stirring
2the water glass of/L, is warming up to 70 DEG C of ageings 2 hours; Use NH
4cl solution presses throw out (butt): ammonium salt: H
2the weight ratio of O=1:0.8:15, at 60 DEG C, ion-exchange removing sodium ion is carried out to sial throw out, exchange and repeat twice, carry out 0.5 hour at every turn, to sodium oxide content lower than 0.3%, more namely drying obtains the mesoporous silicon aluminum described in CN1565733A for 10 hours at 120 DEG C.Be designated as DB-1.
The X-ray diffraction spectrogram of DB-1 is with Fig. 1 feature; Its elementary analytical chemistry consists of 0.15Na
2o72.4Al
2o
326.7SiO
2; Specific surface area 354m
2/ g, pore volume 0.88cm
3/ g, mean pore size 9.9nm.
Comparative example 2
This comparative example illustrates the process of the comparative sample obtained with the pseudo-boehmite of routine and silicon source and phosphorus source reaction modifying.
By a certain amount of industrial pseudo-boehmite (Shandong Aluminum Plant, Al
2o
3content 65wt%) to mix with water by the weight ratio of 1:15 and pull an oar, stir the dilute hydrochloric acid adding metering after 30 minutes, continue stirring and add quantitative tetraethoxy-silicane after 10 minutes, be warming up to 80 DEG C of reactions 4 hours, the phosphoric acid adding metering again continues stirring 1 hour, then at 120 DEG C dry 10 hours, then roasting obtains the comparative sample with structure of similar to thin diaspore in 4 hours at 550 DEG C.Be designated as DB-2.
DB-2 elementary analytical chemistry consists of 0.08Na
2o70.1Al
2o
326.2SiO
23.1P
2o
5; Specific surface area 293m
2/ g, pore volume 0.52cm
3/ g, mean pore size 7.1nm.
Embodiment 7
The present embodiment illustrates that activated silica phosphor-aluminum material provided by the invention is applied to the cracking activity of heavy oil cracking process.
By the activated silica phosphor-aluminum material in each embodiment and REY molecular sieve (RE
2o
316.5%, Na
2o1.4%, Chang Ling catalyst plant is produced) mix mutually by weight the ratio of 1:9, compressing tablet after grinding evenly is also sieved into 20 ~ 40 order particles, 800 DEG C, burin-in process 17 hours under 100% water vapor conditions, heavy oil microreactor carries out cracking performance evaluation, and the micro-anti-appreciation condition of heavy oil is: agent-oil ratio 1.44, sample loading amount 2g, temperature of reaction 500 DEG C, regeneration temperature 600 DEG C, stock oil is vacuum gas oil.Stock oil character is as shown in table 1.Evaluation result is listed in table 2 and table 3.
Comparative example 3
The present embodiment illustrates that the comparative sample material of comparative example 1 and 2 gained is applied to the cracking activity of heavy oil cracking process respectively.
By the material in comparative example 1 and 2 and REY molecular sieve (RE
2o
316.5%, Na
2o1.4%, Chang Ling catalyst plant is produced) mix mutually by weight the ratio of 1:9, compressing tablet after grinding evenly is also sieved into 20 ~ 40 order particles, 800 DEG C, burin-in process 17 hours under 100% water vapor conditions, heavy oil microreactor carries out cracking performance evaluation, and the micro-anti-appreciation condition of heavy oil is with embodiment 7.Evaluation result is listed in table 2.
As can be seen from the heavy oil evaluation result of table 2 and table 3, sample containing activated silica phosphor-aluminum material provided by the invention catalyzer while the coke selectivity that maintenance is good demonstrates more excellent heavy oil cracking performance, cracking activity is higher, heavy oil yield significantly reduces, yield of gasoline improves, product slates optimization.Wherein, transformation efficiency reaches 72.10m% ~ 76.40m%, and heavy oil yield is all down to below 8.69m%, and gasoline yield is increased to more than 50.13m%, and coke/transformation efficiency ratio (burnt turn of ratio), 0.110 ~ 0.115, is all better than comparative sample.
Table 1
Table 2
| Sample number into spectrum | C-1 | C-2 | C-3 | C-DB-1 | C-DB-2 |
| Adding material | MAM-1 | MAM-2 | MAM-3 | DB-1 | DB-2 |
| Material balance/m% | |||||
| Dry gas | 2.09 | 2.18 | 2.14 | 1.98 | 2.17 |
| Liquefied gas | 11.82 | 13.61 | 13.69 | 11.00 | 10.03 |
| Gasoline | 50.13 | 51.80 | 52.07 | 49.59 | 45.71 |
| Diesel oil | 19.21 | 18.94 | 18.76 | 19.82 | 20.24 |
| Heavy oil | 8.69 | 5.14 | 4.99 | 9.19 | 12.33 |
| Coke | 8.06 | 8.33 | 8.35 | 8.42 | 9.53 |
| Transformation efficiency/m% | 72.10 | 75.92 | 76.25 | 70.99 | 67.43 |
| Coke/transformation efficiency | 0.112 | 0.110 | 0.110 | 0.119 | 0.141 |
Table 3
| Sample number into spectrum | C-4 | C-5 | C-6 |
| Adding material | MAM-4 | MAM-5 | MAM-6 |
| Material balance/m% | |||
| Dry gas | 2.23 | 2.09 | 2.06 |
| Liquefied gas | 13.89 | 12.60 | 12.62 |
| Gasoline | 51.73 | 51.03 | 51.22 |
| Diesel oil | 18.56 | 18.08 | 18.51 |
| Heavy oil | 5.04 | 7.67 | 7.15 |
| Coke | 8.55 | 8.53 | 8.44 |
| Transformation efficiency/m% | 76.40 | 74.25 | 74.34 |
| Coke/transformation efficiency | 0.112 | 0.115 | 0.113 |
Claims (15)
1. an activated silica phosphor-aluminum material, is characterized in that this material has pseudo-boehmite crystal phase structure, and its anhydrous compound composition counts (0-0.2) Na with oxide weight ratio
2o(64-76) Al
2o
3(23-35) SiO
2(1-7) P
2o
5, this material specific surface area is 300 ~ 500m
2/ g, pore volume is 0.5 ~ 1.5cm
3/ g, mean pore size is 8 ~ 15nm.
2. according to the silicon phosphor-aluminum material of claim 1, wherein, said specific surface area is 350 ~ 450m
2/ g, pore volume is 0.7 ~ 1.3cm
3/ g, mean pore size is 9 ~ 12nm.
3. a preparation method for activated silica phosphor-aluminum material, is characterized in that comprising following process, by the solution of aluminium source and a kind of alkali mixed plastic the pH value controlling plastic is 7 ~ 11 at room temperature to 85 DEG C; According to SiO
2: Al
2o
3=1:(1.8 ~ 3.5) weight ratio in plastic, add silicon source, ageing 1 ~ 5 hour at room temperature to 90 DEG C; By ageing gained solid sediment and ammonium salt solution or acid solution contact pairs, obtain sodium content lower than 0.3 % by weight solid sediment; Dry with phosphorus source contact pairs and at 100 DEG C ~ 150 DEG C again, or further, roasting at 500 DEG C ~ 700 DEG C, wherein said phosphorus source is with P
2o
5the weight ratio of the butt of meter, its charging capacity and silicon phosphor-aluminum material is (0.01 ~ 0.07): 1.
4. according to the preparation method of claim 3, wherein, said aluminium source is selected from aluminum nitrate, Tai-Ace S 150 or aluminum chloride.
5. according to the preparation method of claim 3, wherein, said alkali is selected from ammoniacal liquor, potassium hydroxide, sodium hydroxide or sodium metaaluminate.
6. according to the preparation method of claim 3, wherein, said silicon source is selected from water glass, water glass, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon or silicon oxide.
7. according to the preparation method of claim 3, wherein, said with ammonium salt solution contact pairs, its process be by ageing gained solid sediment by sedimentary butt: ammonium salt: H
2o=1:(0.1 ~ 1): the weight ratio of (5 ~ 30) exchanges at room temperature to 100 DEG C.
8., according to the preparation method of claim 7, said with ammonium salt contact pairs, its process carries out 1 ~ 3 time, exchanges 0.5 ~ 1 hour at every turn, until in solid sediment sodium content lower than 0.3%.
9. according to the preparation method of claim 3, wherein, said ammonium salt is selected from one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, volatile salt and bicarbonate of ammonia.
10. according to the preparation method of claim 3, wherein, the said process with acid solution contact pairs, be by the solid sediment of ageing gained by sedimentary butt: acid: H
2o=1:(0.03 ~ 0.3): the weight ratio of (5 ~ 30) at least exchanges 0.2 hour at room temperature to 100 DEG C.
11. according to the preparation method of claim 3, and wherein, said acid is selected from sulfuric acid, hydrochloric acid or nitric acid.
12. according to the preparation method of claim 3, wherein, said with phosphorus source contact pairs, its process be by sodium content lower than 0.3 % by weight solid sediment be 1:(5 ~ 20 by the butt of solid sediment with water) weight ratio mix and pull an oar, again phosphorus source to be added in slurries contact pairs at room temperature to 90 DEG C, dry at 100 DEG C ~ 150 DEG C after filtration, washing, and optionally, roasting at 500 DEG C ~ 700 DEG C.
13. according to the preparation method of claim 3, wherein, said with phosphorus source contact pairs, its process be by sodium content lower than 0.3 % by weight solid sediment directly mix with phosphorus source, dry at 100 DEG C ~ 150 DEG C after grinding evenly, and optionally, roasting at 500 DEG C ~ 700 DEG C.
14. according to the preparation method of one of claim 3,12 and 13, and wherein, said phosphorus source is selected from ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate or phosphoric acid.
The activated silica phosphor-aluminum material of 15. claims 1 or 2 in catalytic cracking catalyst or auxiliary agent as the application of active ingredient or active matrix material.
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| CN106732696A (en) * | 2016-12-01 | 2017-05-31 | 中国石油大学(华东) | A kind of magnesium aluminate spinel compoud for being enclosed with silicon phosphorus aluminium lamination and its application |
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| CN109824268A (en) * | 2019-02-25 | 2019-05-31 | 常州市蓝勖化工有限公司 | A kind of preparation method of interface cohesion type high-strength devitrified glass glaze material |
| CN110354874A (en) * | 2019-08-13 | 2019-10-22 | 南开大学 | The preparation method of the sial phosphorus carrier hydrogenation catalyst of porous structure and preparing the application in bio-fuel |
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